FR2765579A1 - NOVEL 4-HYDROXY-2H-1- (THIO) PYRAN-2-ONES DERIVATIVES, THEIR PREPARATIONS AND THEIR USES AS RODONTICIDES - Google Patents

NOVEL 4-HYDROXY-2H-1- (THIO) PYRAN-2-ONES DERIVATIVES, THEIR PREPARATIONS AND THEIR USES AS RODONTICIDES Download PDF

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FR2765579A1
FR2765579A1 FR9708286A FR9708286A FR2765579A1 FR 2765579 A1 FR2765579 A1 FR 2765579A1 FR 9708286 A FR9708286 A FR 9708286A FR 9708286 A FR9708286 A FR 9708286A FR 2765579 A1 FR2765579 A1 FR 2765579A1
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Prior art keywords
hydroxy
bromobiphenyl
benzopyran
radical
formula
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FR9708286A
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French (fr)
Inventor
Jean Jacques Berthelon
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Merck Sante SAS
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LIPHA SAS
LIPHA Liyonnaise Industrielle Pharmaceutique
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Priority to FR9708286A priority Critical patent/FR2765579A1/en
Priority to MA25140A priority patent/MA24582A1/en
Priority to TNTNSN98119A priority patent/TNSN98119A1/en
Priority to PCT/FR1998/001412 priority patent/WO1999001446A1/en
Priority to AU84455/98A priority patent/AU8445598A/en
Publication of FR2765579A1 publication Critical patent/FR2765579A1/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/42—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4
    • C07D311/56—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4 without hydrogen atoms in position 3

Abstract

The invention concerns novel 4-hydroxy-2H-1-(Thio)pyran-2-ones corresponding to formula (I) in which: R1 represents a halogen, a C1-C6 alkoxy radical, a C1-C7 alkyl radical, a trifluoromethyl radical, a cyano radical; R2 represents hydrogen, a C1-C7 alkyl radical, an aralkyl radical, a (hetero)aryl radical, a cyclohexyl radical; R3 and R4 represent hydrogen, a C1-C7 alkyl radical, or together can for a benzene ring, a heterocycle or a -(CH2)n group with n = 3.5; X represents O or S. The compounds are useful as rat poison.

Description

La présente invention concerne des 4-hydroxy-2H-1-(thio)pyran-2-ones, leurThe present invention relates to 4-hydroxy-2H-1- (thio) pyran-2-ones, their

préparationpreparation

et leur utilisation comme rodonticides.  and their use as rodenticides.

L'utilisation des dérivés 4-hydroxy-2H-1-(thio)pyran-2-ones dans la lutte contre les  The use of 4-hydroxy-2H-1- (thio) pyran-2-ones derivatives in the fight against

rongeurs a été décrite dans les brevets US 3 764 693, US 3 957 824, EP 161 163.  rodents has been described in US Patents 3,764,693, US 3,957,824, EP 161,163.

La présente invention a pour objet de nouveaux dérivés de 4-hydroxy-2H-1(thio)pyran- 2-ones représentés par la formule I. R3  The subject of the present invention is new derivatives of 4-hydroxy-2H-1 (thio) pyran- 2-ones represented by formula I. R3

R4/ "X "R4 / "X"

Ri dans laquelle: X représente O ou S, R1 représente l'hydrogène, un halogène, un radical alkoxy en CO-C6, un radical alkyle en C1-C7, un radical trifluorométhyle, un radical cyano, R2 représente l'hydrogène, un radical alkyle en Cl-C7, un radical aralkyle, un radical (hétéro)aryle, un radical cyclohexyle, R3 et R4 représentent l'hydrogène, un radical alkyle en C1-C7 ou peuvent former un cycle  Ri in which: X represents O or S, R1 represents hydrogen, a halogen, a CO-C6 alkoxy radical, a C1-C7 alkyl radical, a trifluoromethyl radical, a cyano radical, R2 represents hydrogen, a C1-C7 alkyl radical, an aralkyl radical, a (hetero) aryl radical, a cyclohexyl radical, R3 and R4 represent hydrogen, a C1-C7 alkyl radical or can form a ring

benzénique, un hétérocycle ou un groupe -(CH2)n- avec n = 3-5.  benzene, a heterocycle or a group - (CH2) n- with n = 3-5.

Le terme alkyle en C1-C7 signifie que le radical peut être linéaire ou ramifié et qu'il peut comprendre de 1 a 7 atomes de carbone tel que méthyle, éthyle, propyle, isopropyle,  The term C1-C7 alkyl means that the radical can be linear or branched and that it can comprise from 1 to 7 carbon atoms such as methyl, ethyl, propyl, isopropyl,

butyle, tert-butyle, isobutyle, pentyle, isopentyle, néopentyle, héxyle, heptyle.  butyl, tert-butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, heptyle.

Le terme " aralkyle " représente un groupement de formule:  The term "aralkyl" represents a group of formula:

RS,(CH2)-RS, (CH2) -

R5R5

avec R5 = H, alkyle en Cl-C7, halogène, alkoxy en C1-C6 et n = 1-3.  with R5 = H, C1-C7 alkyl, halogen, C1-C6 alkoxy and n = 1-3.

Le terme " (hétéro)aryle " représente un cycle aromatique tels que phényle, napthyle,  The term "(hetero) aryl" represents an aromatic ring such as phenyl, naphthyl,

ou un hétérocycle aromatique tels que thiényle, furyle, pyridyle, quinoléinyle.  or an aromatic heterocycle such as thienyl, furyl, pyridyl, quinolinyl.

Le terme " hétérocycle " désigne un cycle à caractère aromatique ou non comprenant 3 à 11 atomes dont 1 à 4 hétéroatomes identiques ou différents choisis parmi l'oxygène, le soufre, et l'azote, comme par exemple furyle, tétrahydrofuryle, thiényle, imidazolyle, quinoléinyle. Les composés de l'invention peuvent contenir des centres chiraux. Les dérivés tels que  The term "heterocycle" designates a ring with an aromatic or non-aromatic character comprising 3 to 11 atoms including 1 to 4 identical or different heteroatoms chosen from oxygen, sulfur and nitrogen, such as, for example, furyl, tetrahydrofuryl, thienyl, imidazolyl , quinolinyl. The compounds of the invention may contain chiral centers. Derivatives such as

les isomères optiques, les racémiques, les énantiomères font parties de l'invention.  optical isomers, racemates, enantiomers are part of the invention.

La demanderesse a trouvé que les composés de formule générale I ont montré une  The Applicant has found that the compounds of general formula I have shown a

réelle activité comme rodonticides, leur propriété essentielle étant un effet anticoagulant.  real activity as rodonticides, their essential property being an anticoagulant effect.

L'activité rodonticide de ce composé a été montré sur des essais effectués sur des  The rodonticidal activity of this compound has been shown in tests carried out on

rongeurs sauvages (Rattus Norvegicus, Mus-Musculus).  wild rodents (Rattus Norvegicus, Mus-Musculus).

Pour cela un appât dosé à 25 ppm en substance à examiner est préparé par imprégnation de blé méthode OEPP. Cet appât est ensuite donné pendant 3 jours à des rongeurs sauvages mâles ou femelles. L'activité est examinée en déterminant la  For this, a bait dosed at 25 ppm of substance to be examined is prepared by impregnation of wheat EPPO method. This bait is then given for 3 days to wild male or female rodents. The activity is examined by determining the

I0 mortalité.I0 mortality.

A titre d'exemple le composé de l'exemple 1 à la dose de 25 ppm administré à des rats  By way of example, the compound of Example 1 at the dose of 25 ppm administered to rats

sauvages (Rattus Norvegicus), a entraîné une mortalité de 100 %.  wild (Rattus Norvegicus), resulted in 100% mortality.

Parmi les composés préférés de la formule I on peut citer par exemple: 3(4-(4-bromophényl)-benzyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1-(4'bromobiphényl-4-yl)-ethyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1 -(4'bromobiphényl-4-yl)-pentyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1 -(4'bromobiphényl-4-yl)-1 -cyclohexyl-méthyl)-4-hydroxy-2H-1 -benzopyran-2one 3-(1 -(4'-bromobiphényl-4-yl)-2-méthyl-propyl)-4-hydroxy-2H-1 benzopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 benzothiopyran-2-one 3-((1-(4'-bromobiphényl-4-yl)-2-phényl)-éthyl)-4hydroxy-2H-1 -benzopyran-2-one 3-((1 I-(4'-bromobiphényl-4-yl)-3-méthyl)butyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-33-diméthyl-butyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1 -(4'fluorobiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1-(4'trifluorométhylbiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-pentyl)-4-hydroxy-2H-1 -benzothiopyran-2- one 3-(1-(4'-méthylbiphényle-4-yl)-éthyl)-4-hydroxy-1 -benzopyran-2-one 3-(1 -(4'-isopropylbiphényl-4-yl)-éthyl)-4-hydroxy-1 -benzopyran-2-one 3- (1 -(4'cyanobiphényl-4-yl)-éthyl)-4-hydroxy-1 -benzopyran-2-one 3-(-1 (4'-bromobiphényl-4-yl)-3-méthyl-butyl)-4-hydroxy-2H-1 -benzothiopyran-2one 3-(-1-(4'-bromobiphényl-4-yl)-propyl)-4-hydroxy-2H-1 -benzopyran2-one 3-(-1 -(4'-bromobiphényl-4-yl)-méthyl-pentyl)-4-hydroxy-2H-1 benzopyran-2-one 3-(1-(4'-bromobiphényl-4-yl)-propyl)-4-hydroxy-2H-1 benzothiopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-butyl)-4-hydroxy-2H-1 -benzothiopyran-2-one 3-(1 -(4'-bromodiphényl-4-yl)-butyl)-4-hydroxy-2H- 1 -benzopyran-2-one 3 L'invention vise également un procédé de préparation des composés de formule I. Celui-ci est résumé dans le schéma 1 À Schema 1  Among the preferred compounds of formula I, there may be mentioned for example: 3 (4- (4-bromophenyl) -benzyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1- (4'bromobiphenyl- 4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzopyran-2 -one 3- (1 - (4'bromobiphenyl-4-yl) -1 -cyclohexyl-methyl) -4-hydroxy-2H-1 -benzopyran-2one 3- (1 - (4'-bromobiphenyl-4-yl) -2-methyl-propyl) -4-hydroxy-2H-1 benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 benzothiopyran-2- one 3 - ((1- (4'-bromobiphenyl-4-yl) -2-phenyl) -ethyl) -4hydroxy-2H-1 -benzopyran-2-one 3 - ((1 I- (4'-bromobiphenyl- 4-yl) -3-methyl) butyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -33-dimethyl-butyl) -4- hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'fluorobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1- (4 ' trifluoromethylbiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 - benzothiopyran-2- one 3- ( 1- (4'-methylbiphenyl-4-yl) -ethyl) -4-hydroxy-1 -benzopyran-2-one 3- (1 - (4'-isopropylbiphenyl-4-yl) -ethyl) -4-hydroxy- 1 -benzopyran-2-one 3- (1 - (4'cyanobiphenyl-4-yl) -ethyl) -4-hydroxy-1 -benzopyran-2-one 3 - (- 1 (4'-bromobiphenyl-4-yl ) -3-methyl-butyl) -4-hydroxy-2H-1 -benzothiopyran-2one 3 - (- 1- (4'-bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H-1 -benzopyran2- one 3 - (- 1 - (4'-bromobiphenyl-4-yl) -methyl-pentyl) -4-hydroxy-2H-1 benzopyran-2-one 3- (1- (4'-bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H-1 benzothiopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -butyl) -4-hydroxy-2H-1 -benzothiopyran-2-one 3- (1 - (4'-bromodiphenyl-4-yl) -butyl) -4-hydroxy-2H- 1 -benzopyran-2-one 3 The invention also relates to a process for the preparation of the compounds of formula I. This is summarized in Figure 1 TO Figure 1

Stade I1-Stage I1-

R / \CI- R2 R2R / \ CI- R2 R2

R - R IV Stade 2: RR IV V Stade 3: OH R  R - R IV Stage 2: RR IV V Stage 3: OH R

I*R, RI * R, R

R4 O OHR4 O OH

VI VVI V

OH Rz R3 (11R Dans le stade 1 on fait réagir un dérivé biphénylique (Il) avec un chlorure d'acide (111), notamment dans un solvant comme le sulfure de carbone ou le chlorure de méthylène et  OH Rz R3 (11R In stage 1, a biphenyl derivative (II) is reacted with an acid chloride (111), in particular in a solvent such as carbon sulphide or methylene chloride and

en présence de chlorure d'aluminium.  in the presence of aluminum chloride.

Dans le stade 2 on réduit le groupement cétonique en alcool, notamment à l'aide du borohydrure de sodium, dans un solvant tel que l'éthanol, le méthanol.  In stage 2, the ketone group is reduced to alcohol, in particular using sodium borohydride, in a solvent such as ethanol, methanol.

Dans le stade 3 on condense le dérivé alcoolique avec une 4-hydroxy-2H-1(thio)pyran-  In stage 3, the alcoholic derivative is condensed with a 4-hydroxy-2H-1 (thio) pyran-

2-one, notamment dans un solvant tel que l'acide acétique, en présence d'acide sulfurique et à une température comprise entre 20 C et 150 C. Les composés de l'invention possèdent d'excellentes propriétés rodonticides comme  2-one, in particular in a solvent such as acetic acid, in the presence of sulfuric acid and at a temperature between 20 C and 150 C. The compounds of the invention have excellent rodonticidal properties such as

ceci a pu être montré dans des essais effectués chez les rongeurs sauvages.  this has been shown in tests with wild rodents.

Les composés de l'invention et en particulier le composé de l'exemple 1 constituent des substances actives anticoagulantes de composition rodonticides en association avec un  The compounds of the invention and in particular the compound of Example 1 constitute anticoagulant active substances of rodonticidal composition in combination with a

support consommable par les rongeurs.  support consumable by rodents.

Il est donné ci-après des exemples qui illustrent l'invention à titre non limitatif: l s Exemple I: 3-(1-4'-Bromobiphényl-4-yl)-3-méthylbutyl)-4-hydroxy-2H-1-benzopyran-2-one C26H23BrO3 PM = 463,38 Br a) On solubilise 559,2 g (2,4 moles) de 4- bromobiphényle dans 3,6 litres de chlorure de méthylène. On ajoute ensuite en 15 minutes 304,8 ml (2,4 moles) de chlorure d'isovaléryle. On refroidit à 10 C et on additionne en 1 heure 352,8 g (2,6 moles) de chlorure d'aluminium. On amène la température à 21 C et on porte sous agitation 3 heures à cette température. On verse dans 15 litres d'eau contenant 0,5 litre d'acide chlorhydrique concentré. On décante, on extrait avec 2 x 1,5 litres de chlorure de méthylène, on lave avec 5 litres de soude à 10 % puis avec 5 litres d'eau. Après  Examples are given below which illustrate the invention without limitation: ls Example I: 3- (1-4'-Bromobiphenyl-4-yl) -3-methylbutyl) -4-hydroxy-2H-1- benzopyran-2-one C26H23BrO3 PM = 463.38 Br a) 559.2 g (2.4 moles) of 4-bromobiphenyl are dissolved in 3.6 liters of methylene chloride. Then added in 15 minutes 304.8 ml (2.4 moles) of isovaleryl chloride. The mixture is cooled to 10 ° C. and 352.8 g (2.6 moles) of aluminum chloride are added over 1 hour. The temperature is brought to 21 ° C. and the mixture is brought to stirring for 3 hours at this temperature. Pour into 15 liters of water containing 0.5 liters of concentrated hydrochloric acid. Decanted, extracted with 2 x 1.5 liters of methylene chloride, washed with 5 liters of 10% sodium hydroxide and then with 5 liters of water. After

décantation et séchage on concentre sous vide. On obtient 661 g de 1-(4'-  decantation and drying are concentrated under vacuum. We obtain 661 g of 1- (4'-

bromobiphényl-4-yl)-3-méthyl-1-oxo-butane que l'on recristallise dans l'éthanol.  bromobiphenyl-4-yl) -3-methyl-1-oxo-butane which is recrystallized from ethanol.

Poids obtenu: 518 g (Rdt: 68 %)Weight obtained: 518 g (Yield: 68%)

PFK = 100 CPFK = 100 C

lRPc=o0: 1680 cm-1 b) On place 158,5 g (0,5 mole) de 1-(4'-bromobiphényl4-yl)-3-méthyl-1-oxo-butane dans 2 litres d'éthanol. On porte au reflux sous agitation pour solubiliser. On ajoute ensuite 150 g de Kataboran (solution alcaline de borohydrure de sodium) et on maintient le reflux pendant 2 heures. Un précipité blanc se forme. On laisse 1 heure sous agitation à température ambiante. On verse dans 15 litres d'eau. Après extraction avec 2 x 3 litres de chlorure de méthylène, lavage avec 10 litres d'eau et séchage, la phase organique est concentrée sous vide a 40 C. On obtient 153 g de  lRPc = o0: 1680 cm-1 b) 158.5 g (0.5 mole) of 1- (4'-bromobiphenyl4-yl) -3-methyl-1-oxo-butane are placed in 2 liters of ethanol. The mixture is brought to reflux with stirring to dissolve. 150 g of Kataboran (alkaline sodium borohydride solution) are then added and the reflux is maintained for 2 hours. A white precipitate forms. The mixture is left stirring for 1 hour at room temperature. We pour in 15 liters of water. After extraction with 2 x 3 liters of methylene chloride, washing with 10 liters of water and drying, the organic phase is concentrated under vacuum at 40 C. 153 g of

1-(4'-bromobiphényl-4-yl)-1 -hydroxy-3-méthyl-butane.  1- (4'-bromobiphenyl-4-yl) -1-hydroxy-3-methyl-butane.

Rdt: 95,8 %YId: 95.8%

PFK = 95 CPFK = 95 C

IRyOH: 3350 cm-'IRyOH: 3350 cm- '

c) On solubilise 166 g (0,52 mole) de 1-(4'-bromobiphényl-4-yl)-1hydroxy-3-méthyl-  c) 166 g (0.52 mole) of 1- (4'-bromobiphenyl-4-yl) -1hydroxy-3-methyl- are dissolved.

butane et 100,7 g (0,61 mole) de 4-hydroxycoumarine dans 1,4 litres d'acide acétique. On porte à reflux et on ajoute en 30 minutes 14,2 ml d'acide sulfurique concentré. On maintient le reflux pendant 2 heures. On refroidit puis on verse dans 17 litres d'eau. On extrait avec 10 I d'éther éthylique. Après décantation la phase organique est reprise par 6 litres de soude à 10 %. Une couche huileuse se forme entre la phase éthérée et la phase aqueuse. On isole cette huile que l'on dissout dans 5 litres d'acétate d'éthyle. On traite ensuite avec 2,5 litres d'acide chlorhydrique 1/2, on décante, lave la phase organique à l'eau, sèche et concentre sous vide, on obtient 142 g du produit de l'exemple 1. Après recristallisation dans l'acide acétique,  butane and 100.7 g (0.61 mole) of 4-hydroxycoumarin in 1.4 liters of acetic acid. The mixture is brought to reflux and 14.2 ml of concentrated sulfuric acid are added over 30 minutes. The reflux is maintained for 2 hours. It is cooled and then poured into 17 liters of water. Extraction is carried out with 10 l of ethyl ether. After decantation, the organic phase is taken up in 6 liters of 10% sodium hydroxide. An oily layer forms between the ethereal phase and the aqueous phase. This oil is isolated and dissolved in 5 liters of ethyl acetate. Then treated with 2.5 liters of 1/2 hydrochloric acid, decanted, washed the organic phase with water, dried and concentrated in vacuo, 142 g of the product of Example 1 are obtained. After recrystallization from 1 'acetic acid,

on obtient 119,5 g d'un solide blanc.  119.5 g of a white solid are obtained.

Rdt: 49,6 %YId: 49.6%

PFG = 172-175 CPFG = 172-175 C

IRóc=o: 1668 cm"1 IRYoH: 3256 cm-1 1H RMN (CDCI3) ô en ppm: 1,04 (dd, 2CH3); 1,63-1,67 (m, CH); 2,15-19,4 (m, CH2); 4,72 (m, CH); 6,3 (s, OH); 7,24-7,7 (m, 12 AR) Analyse pondérale: C% H% Br%/0 0% Calculée 67,39 5,00 17,24 10,36 Trouvée 67,13 5,07 16,99  IRóc = o: 1668 cm "1 IRYoH: 3256 cm-1 1H NMR (CDCI3) ô in ppm: 1.04 (dd, 2CH3); 1.63-1.67 (m, CH); 2.15-19 , 4 (m, CH2); 4.72 (m, CH); 6.3 (s, OH); 7.24-7.7 (m, 12 AR) Weight analysis: C% H% Br% / 0 0% Calculated 67.39 5.00 17.24 10.36 Found 67.13 5.07 16.99

Exemple 2:Example 2:

3-(4-(4-Bromophényl)-benzyl)-4-hydroxy-2H-1 -benzopyran-2-one C22H15BrO3 PM = 407,27 OH Br  3- (4- (4-Bromophenyl) -benzyl) -4-hydroxy-2H-1 -benzopyran-2-one C22H15BrO3 PM = 407.27 OH Br

PFG = 275-279 CPFG = 275-279 C

IRyc=o 1670 cm1 IRyOH: 3250 cm' 1H RMN (DMSO) 6 en ppm 4,07 (s, CH2); 7,47-8,15 (m, 12 AR) Analyse pondérale: C% H% Br%/ Calculée 64,88 3,71 19,62 Trouvée 64,64 3,79 19,29  IRyc = o 1670 cm1 IRyOH: 3250 cm '1H NMR (DMSO) 6 in ppm 4.07 (s, CH2); 7.47-8.15 (m, 12 AR) Weight analysis: C% H% Br% / Calculated 64.88 3.71 19.62 Found 64.64 3.79 19.29

Exemple 3:Example 3:

3-(1 -(4'-Bromobiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 -benzopyran-2-one C23H17BrO3 PM = 421,29 OH Br  3- (1 - (4'-Bromobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one C23H17BrO3 PM = 421.29 OH Br

PFG= 204-212 CPFG = 204-212 C

lIRmo: 1680 cm' IRYoH: 3250 cm1 1H RMN (CDCI3) 5 en ppm: 1,51 (d, CH3); 4,58 (q, CH); 5,87 (s, OH); 7,05-7,5 (m, 12 AR) Analyse pondérale: C% H% Br% Calculée 65,57 4,07 18,97 Trouvée 65,81 3,88 19,17  IRmo: 1680 cm 'IRYoH: 3250 cm1 1H NMR (CDCI3) 5 in ppm: 1.51 (d, CH3); 4.58 (q, CH); 5.87 (s, OH); 7.05-7.5 (m, 12 AR) Weight analysis: C% H% Br% Calculated 65.57 4.07 18.97 Found 65.81 3.88 19.17

Exemple 4:Example 4:

3-(1-(4'-Bromobiphényl-4-yl)-pentyl)-4-hydroxy-2H-1 -benzopyran-2-one C26H23BrO3 PM = 463,38 OHX Br o PFG = 146-150 C I R4.=o: 1680 cm' IRoH: 3250 cm1 1H RMN (CDCI3) 5 en ppm 0,97 (t, CH3); 1,5 (m, 2CH2); 2,24 (m, CH2) 4,69 (t, CH); 6,65 (s, OH); 7,31-7,81 (m, 12 AR) Analyse Dondérale: C% H% Br%/o Calculée 67,39 5,00 17,25 Trouvée 67,19 4, 80 16,94  3- (1- (4'-Bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzopyran-2-one C26H23BrO3 PM = 463.38 OHX Br o PFG = 146-150 CI R4. = o: 1680 cm 'IRoH: 3250 cm1 1H NMR (CDCI3) 5 in ppm 0.97 (t, CH3); 1.5 (m, 2CH2); 2.24 (m, CH2) 4.69 (t, CH); 6.65 (s, OH); 7.31-7.81 (m, 12 AR) Dondérale Analysis: C% H% Br% / o Calculated 67.39 5.00 17.25 Found 67.19 4.80 16.94

Exemple 5:Example 5:

3-(1 -(4'-Bromobiphényl-4-yl)-1 -cyclohexyl-méthyl)-4-hydroxy-2H-1 benzopyran-2-  3- (1 - (4'-Bromobiphenyl-4-yl) -1 -cyclohexyl-methyl) -4-hydroxy-2H-1 benzopyran-2-

one C28H25BrO3 PM = 489,41 OHX Brone C28H25BrO3 PM = 489.41 OHX Br

PFG = 205-209 CPFG = 205-209 C

IR.yc,=o: 1660 cm-' IROH: 3250 cm-' 1H RMN (DMSO) 6 en ppm:1-1,85 (m, 5CH2); 2,9-3 (m, CH); 4,35 (m, CH); 7,52-8,23 (m, 12 AR) Analyse pondérale: C% H% BrI/o Calculée 68,71 5,15 16,33 l0 Trouvée 68,41 5,24 16,33  IR.yc, = o: 1660 cm- 'IROH: 3250 cm-' 1H NMR (DMSO) 6 in ppm: 1-1.85 (m, 5CH2); 2.9-3 (m, CH); 4.35 (m, CH); 7.52-8.23 (m, 12 AR) Weight analysis: C% H% BrI / o Calculated 68.71 5.15 16.33 l0 Found 68.41 5.24 16.33

Exemple 6:Example 6:

3-(1 -(4'-Bromobiphényl-4-yl)-2-méthyl-propyl)-4-hydroxy-2H-1 benzopyran-2-one C25H21BrO3 PM = 449,35 OH Br  3- (1 - (4'-Bromobiphenyl-4-yl) -2-methyl-propyl) -4-hydroxy-2H-1 benzopyran-2-one C25H21BrO3 PM = 449.35 OH Br

PFG = 163-168 CPFG = 163-168 C

I Ryc=o: 1670 cm1 IRrOH: 3250 cm" 1H RMN (CDCI3) 6 en ppm: 1,28 (d, 2CH3); 3,23 (m, CH); 4,4 (m, CH); 7,31-8,02 (m,  I Ryc = o: 1670 cm1 IRrOH: 3250 cm "1H NMR (CDCI3) 6 in ppm: 1.28 (d, 2CH3); 3.23 (m, CH); 4.4 (m, CH); 7, 31-8.02 (m,

12 AR)12 AR)

Analyse pondérale: C% H% Br% Calculée 66,82 4,71 17,79 Trouvée 67,07 4,82 17,69  Weight analysis: C% H% Br% Calculated 66.82 4.71 17.79 Found 67.07 4.82 17.69

Exemple 7:Example 7:

3-(1 -(4'-Bromobiphényl-4-yl)-éthyl-4-hydroxy-2H-1 -benzothiopyran-2-one C23H17BrO2S PM = 437,36 OH g' OBr  3- (1 - (4'-Bromobiphenyl-4-yl) -ethyl-4-hydroxy-2H-1 -benzothiopyran-2-one C23H17BrO2S PM = 437.36 OH g 'OBr

PFG= 138-140 CPFG = 138-140 C

IRP,.o: 1580 cm'1 IRyOH: 3330 cm1 1H RMN (CDCI3) ô en ppm: 1,67 (d, 2CH3); 5,14 (q, CH); 6,16 (s, OH); 7,27-8,01 (m,  IRP, .o: 1580 cm'1 IRyOH: 3330 cm1 1H NMR (CDCI3) ô in ppm: 1.67 (d, 2CH3); 5.14 (q, CH); 6.16 (s, OH); 7.27-8.01 (m,

12 AR)12 AR)

0o Analyse pondérale: C% H% Br% S% Calculée 63,16 3,92 18,27 7,33 Trouvée 63,02 3,89 17,83 7,25  0o Weight analysis: C% H% Br% S% Calculated 63.16 3.92 18.27 7.33 Found 63.02 3.89 17.83 7.25

Exemple 8:Example 8:

1i 5 3-(1 -(4'-Bromobiphényl-4-yl)-2-phényl-éthyl)-4-hydroxy-2H-1 benzopyran-2-one C29H21BrO3 PM = 497,39 OH Br  1i 5 3- (1 - (4'-Bromobiphenyl-4-yl) -2-phenyl-ethyl) -4-hydroxy-2H-1 benzopyran-2-one C29H21BrO3 PM = 497.39 OH Br

PFG = 221-226 CPFG = 221-226 C

IRyc=o: 1665 cm'1 IRFOH: 3150 cm'IRyc = o: 1665 cm'1 IRFOH: 3150 cm '

1H RMN (DMSO) ô en ppm: 3,17-3,23 (m, CH); 3,42-3,5 (m, CH); 4,66 (m, CH); 6,85-  1H NMR (DMSO) ô in ppm: 3.17-3.23 (m, CH); 3.42-3.5 (m, CH); 4.66 (m, CH); 6.85-

7,7 (m, 17 AR) Analyse pondérale: C% H% Br% Calculée 70,03 4,26 16,07 Trouvée 69,99 4,26 15,93  7.7 (m, 17 AR) Weight analysis: C% H% Br% Calculated 70.03 4.26 16.07 Found 69.99 4.26 15.93

Exemple 9:Example 9:

3-(-1 -(4'-Bromobiphényl-4-yl)-3-3-diméthyl-butyl)-4-hydroxy-2H-1 benzopyran-2-  3 - (- 1 - (4'-Bromobiphenyl-4-yl) -3-3-dimethyl-butyl) -4-hydroxy-2H-1 benzopyran-2-

one C27H25BrO3 PM = 477,40one C27H25BrO3 PM = 477.40

OH /OH /

BrBr

PFG = 233-235 CPFG = 233-235 C

I1R C=o:1675 cm-1 IRPOH: 3180 cm' H RMN (DMSO) 6 en ppm 0,67 (s, 3CH3); 1,78-1,84 (dd, CH); 2,18-2,26 (dd, CH) 4,38 (m, CH); 7,1-7,83 (m, 12 AR) Analyse pondérale: C% H% Br/o Calculée 67, 93 5,28 16,74 Trouvée 67,97 5,30 16,59  I1R C = o: 1675 cm-1 IRPOH: 3180 cm 'H NMR (DMSO) 6 in ppm 0.67 (s, 3CH3); 1.78-1.84 (dd, CH); 2.18-2.26 (dd, CH) 4.38 (m, CH); 7.1-7.83 (m, 12 AR) Weight analysis: C% H% Br / o Calculated 67, 93 5.28 16.74 Found 67.97 5.30 16.59

Exemple 10:Example 10:

3-(1 -(4'-Fluorobiphényl-4-yl)-ethyl)-4-hydroxy-2H-1-benzopyran-2-one  3- (1 - (4'-Fluorobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1-benzopyran-2-one

C23H17FO3 PM = 360,39C23H17FO3 PM = 360.39

OH 1lOH 1l

PFG = 168-170 CPFG = 168-170 C

IRyc=o: 1670 cm' IRoH: 3250 cm' 1H RMN (CDCI3) 5 en ppm: 1,75 (d, 3CH3) 4,82 (q, CH); 6,38 (s, OH); 7,15-7,77 (m,  IRyc = o: 1670 cm 'IRoH: 3250 cm' 1H NMR (CDCI3) 5 in ppm: 1.75 (d, 3CH3) 4.82 (q, CH); 6.38 (s, OH); 7.15-7.77 (m,

12 AR)12 AR)

Analyse pondérale: C% H% Br% Calculée 76, 65 4,76 5,27 Trouvée 76,41 4,98 5,28  Weight analysis: C% H% Br% Calculated 76, 65 4.76 5.27 Found 76.41 4.98 5.28

Exemple 11:Example 11:

3-(1 -(4'-Trifluorométhylbiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 benzopyran-2-one  3- (1 - (4'-Trifluoromethylbiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 benzopyran-2-one

C24H17F303 PM = 410,40C24H17F303 PM = 410.40

OHOH

15....CF315 .... CF3

PFG = 207-209 CPFG = 207-209 C

IRrc=o: 1675 cm-' IRyOH: 3230 cm' 1H RMN (CDCI3) 5 en ppm: 1,58 (d, CH3); 4,65 (q, CH); 5,92 (s, OH); 7,1-7,56 (m, 12 AR) Analyse pondérale:  IRrc = o: 1675 cm- 'IRyOH: 3230 cm' 1H NMR (CDCI3) 5 in ppm: 1.58 (d, CH3); 4.65 (q, CH); 5.92 (s, OH); 7.1-7.56 (m, 12 AR) Weight analysis:

C% H% F%C% H% F%

Calculée 70,24 4,18 13,89 Trouvée 69,95 4,10 13,96  Calculated 70.24 4.18 13.89 Found 69.95 4.10 13.96

Exemple 12:Example 12:

3-(1 -(4'-Bromobiphényl-4-yl)-pentyl)-4-hydroxy-2H-1 -benzothiopyran-2one C26H23BrO2S PM = 479,44 OH Br  3- (1 - (4'-Bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzothiopyran-2one C26H23BrO2S PM = 479.44 OH Br

PFG = 136-137 CPFG = 136-137 C

IRYc=o: 1590 cm" IRyOH: 3250 cm-1 'H RMN (CDCI3) 6 en ppm: 0,93 (t, CH3); 1,44 (m, 2CH2); 2-2,27 (m, CH2); 5,5 (t, CH); 6,24 (s, OH); 7,28-8, 03 (m, 12 AR) Analyse pondérale: C% H% Br%/ S% Calculée 65,13 4,84 16,67 6,69 Trouvée 64,86 5,01 16,68 6,86  IRYc = o: 1590 cm "IRyOH: 3250 cm-1 'H NMR (CDCI3) 6 in ppm: 0.93 (t, CH3); 1.44 (m, 2CH2); 2-2.27 (m, CH2 ); 5.5 (t, CH); 6.24 (s, OH); 7.28-8.03 (m, 12 AR) Weight analysis: C% H% Br% / S% Calculated 65.13 4 , 84 16.67 6.69 Found 64.86 5.01 16.67 6.86

Exemple 13:Example 13:

3-1 -(4'-Méthylbiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 -benzopyran-2-one  3-1 - (4'-Methylbiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one

C24H2003 PM = 356,43C24H2003 PM = 356.43

OHOH

PFG = 227-231 0 CPFG = 227-231 0 C

IRyc=o: 1670 cm' IRyoH: 3230 cm1 H RMN (DMSO) 6 en ppm: 1,57 (d, CH3); 2, 24 (s, CH3); 4,55 (m, CH); 7,15-7,95 (m,  IRyc = o: 1670 cm 'IRyoH: 3230 cm1 H NMR (DMSO) 6 in ppm: 1.57 (d, CH3); 2.24 (s, CH3); 4.55 (m, CH); 7.15-7.95 (m,

12 AR)12 AR)

Analyse pondérale:Weight analysis:

C% H%C% H%

Calculée 80,88 5,66 Trouvee 80,64 5,80  Calculated 80.88 5.66 Found 80.64 5.80

Exemple 14:Example 14:

3-(1 -(4'-Isopropylbiphényl-4-yl)-ethyl)-4-hydroxy-2H-benzopyran-2-one  3- (1 - (4'-Isopropylbiphenyl-4-yl) -ethyl) -4-hydroxy-2H-benzopyran-2-one

C26H2403 PM = 384,48C26H2403 PM = 384.48

OHOH

PFG = 210-220 CPFG = 210-220 C

IRyc=o: 1675 cm1 IRyOH: 3230 cm-' 1H RMN (CDCI3) 5 en ppm: 1,31 (d, 2CH3); 1,66 (d, CH3); 2,98 (m, CH); 4,78 (m, CH); 6,08 (s, OH); 7,22-7, 70 (m, 12 AR) Analyse pondérale:  IRyc = o: 1675 cm1 IRyOH: 3230 cm- '1H NMR (CDCI3) 5 in ppm: 1.31 (d, 2CH3); 1.66 (d, CH3); 2.98 (m, CH); 4.78 (m, CH); 6.08 (s, OH); 7.22-7.70 (m, 12 AR) Weight analysis:

C% H%C% H%

Calculée 81,22 6,29 Trouvée 81,28 6,34  Calculated 81.22 6.29 Found 81.28 6.34

Exemple 15:Example 15:

3-(1 -(4'-Cyanobiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 -benzopyran-2-one  3- (1 - (4'-Cyanobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one

C24H17NO3 PM = 367,41C24H17NO3 PM = 367.41

OH NOH N

PFG = 227-230 CPFG = 227-230 C

IRyc.0: 1665 cm' IRyOH: 3180 cm" 1H RMN (CDCI3) 5 en ppm: 1,75 (d, CH3); 4,80 (q, CH); 5,95 (s, OH); 7,26-7,78 (m, 12 AR) Analyse pondérale  IRyc.0: 1665 cm 'IRyOH: 3180 cm "1H NMR (CDCI3) 5 in ppm: 1.75 (d, CH3); 4.80 (q, CH); 5.95 (s, OH); 7, 26-7.78 (m, 12 AR) Weight analysis

C% H% N%C% H% N%

Calculée 78,46 4,66 3,81 Trouvée 78, 37 4,63 3,75  Calculated 78.46 4.66 3.81 Found 78, 37 4.63 3.75

Exemple 16:Example 16:

3-(-1 -(4'-Bromobiphényl-4-yl)-3-méthyl-butyl)-4-hydroxy-2H-1 benzothiopyran-2-  3 - (- 1 - (4'-Bromobiphenyl-4-yl) -3-methyl-butyl) -4-hydroxy-2H-1 benzothiopyran-2-

one C26H23BrO2S PM = 479,44 OH yone C26H23BrO2S PM = 479.44 OH y

PFG = 105-106 CPFG = 105-106 C

IRyc=o: 1590 cm-1 1H RMN (CDCI3) b en ppm: 1,04 (d,d, 2CH3); 1,63 (m, CH); 1,93-2,11 (m, CH2); 5,16 (m, CH); 6,25 (s, OH); 7,2-8,02 (m, 12 AR) Analyse pondérale: C% H% Br% S% Calculée 65,13 4,84 16,67 6,69 Trouvée 65,27 4,95 16,54 6,91  IRyc = o: 1590 cm-1 1H NMR (CDCI3) b in ppm: 1.04 (d, d, 2CH3); 1.63 (m, CH); 1.93-2.11 (m, CH2); 5.16 (m, CH); 6.25 (s, OH); 7.2-8.02 (m, 12 AR) Weight analysis: C% H% Br% S% Calculated 65.13 4.84 16.67 6.69 Found 65.27 4.95 16.54 6.91

Exemple 17:Example 17:

33-1 -(4'-Bromobiphényl-4-yl)-propyl)-4-hydroxy-2H-1 -benzopyran-2-one C24H19BrO3 PM = 435,3 OH/ CSA00  33-1 - (4'-Bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H-1 -benzopyran-2-one C24H19BrO3 PM = 435.3 OH / CSA00

PFG = 194-195 CPFG = 194-195 C

IR.c=o: 1670 cm' IRroH: 3270 cm'1 1H RMN (DMSO) 6 en ppm: 0,81 (t, CH3); 2,01-2,4 (m, CH2) 4,31 (m, CH) 7,09-7,95 (m, 12 AR) Analyse pondérale: C% H% Br/o Calculée 66,22 4,40 18,36 !o Trouvée 66,34 4,22 18,08  IR.c = o: 1670 cm 'IRroH: 3270 cm'1 1H NMR (DMSO) 6 in ppm: 0.81 (t, CH3); 2.01-2.4 (m, CH2) 4.31 (m, CH) 7.09-7.95 (m, 12 AR) Weight analysis: C% H% Br / o Calculated 66.22 4.40 18.36! O Found 66.34 4.22 18.08

Exemple 18:Example 18:

3-(-1 -4'-Bromobiphényl-4-yl)-4-méthyl-pentyl)-4-hydroxy-2H-1 benzopyran-2-one C27H25BrO3 PM = 477,40 OH Br  3 - (- 1 -4'-Bromobiphenyl-4-yl) -4-methyl-pentyl) -4-hydroxy-2H-1 benzopyran-2-one C27H25BrO3 PM = 477.40 OH Br

PFG = 203-206 CPFG = 203-206 C

IRc.o: 1680 cm' IRoH: 3200 cm" 1H RMN (CDCI3) 6 en ppm: 1,15 (d,d, 2CH3); 1,58 (m, CH2) 1,86 (m, CH) 2,36 (m, CH2); 4,83 (t, CH); 6,62 (s, OH); 7, 49-7,96 (m, 12 AR) Analyse Dondérale: C% H% Br/o Calculée 67,93 5,28 16,74 Trouvée 68,33 5,21 16,90  IRc.o: 1680 cm 'IRoH: 3200 cm "1H NMR (CDCI3) 6 in ppm: 1.15 (d, d, 2CH3); 1.58 (m, CH2) 1.86 (m, CH) 2, 36 (m, CH2); 4.83 (t, CH); 6.62 (s, OH); 7.49-7.96 (m, 12 AR) Dondérale Analysis: C% H% Br / o Calculated 67 .93 5.28 16.74 Found 68.33 5.21 16.90

Exemple 19:Example 19:

3-(1 -4'-Bromobiphényl-4-yl)-propyl)-4-hydroxy-2H-1 -benzothiopyran-2- one C24H19BrO2S PM = 451,39 OH Br  3- (1 -4'-Bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H-1 -benzothiopyran-2- one C24H19BrO2S PM = 451.39 OH Br

PFG = 177-181 CPFG = 177-181 C

IRc=o: 1590 cm-1 IRyOH: 3230 cm-1 1H RMN (CDC13) 8 en ppm: 1,25 (t, CH3); 2,18-2,56 (m, CH2); 5,15 (m, CH); 6,4 (s, OH); 7,37-8,19 (m, 12 AR) Analyse pondérale: C% H% Br/o S% Calculée 63,86 4,24 17,71 7,10 1o Trouvée 63,93 4,14 17,41 7,06  IRc = o: 1590 cm-1 IRyOH: 3230 cm-1 1H NMR (CDC13) 8 in ppm: 1.25 (t, CH3); 2.18-2.56 (m, CH2); 5.15 (m, CH); 6.4 (s, OH); 7.37-8.19 (m, 12 AR) Weight analysis: C% H% Br / o S% Calculated 63.86 4.24 17.71 7.10 1o Found 63.93 4.14 17.41 7 . 06

Exemple 20:Example 20:

3-(1 -(4'-Bromobiphényl-4-yl)-butyl)-4-hydroxy-2H-1 -benzothiopyran-2- one C25J21BrO2S PM = 462,41 OHJ v - Br  3- (1 - (4'-Bromobiphenyl-4-yl) -butyl) -4-hydroxy-2H-1 -benzothiopyran-2- one C25J21BrO2S PM = 462.41 OHJ v - Br

PFG=134-136 CPFG = 134-136 C

IRYc=o: 1590 cm-' IRyOH: 3425 cm1 H RMN (CDCI3) 5 en ppm: 0,92 (t, CH3); 1,41 (m, CH2); 1,96 (m, CH2); 4,98 (m, CH); 6,17 (s, OH); 7,26-7,93 (m, 12 AR) Analyse pondérale: C% H% Br/o S% Calculée 64,52 4,55 17,17 6,89 Trouvée 64,52 4,52 17,04 6,55  IRYc = o: 1590 cm- 'IRyOH: 3425 cm1 H NMR (CDCI3) 5 in ppm: 0.92 (t, CH3); 1.41 (m, CH2); 1.96 (m, CH2); 4.98 (m, CH); 6.17 (s, OH); 7.26-7.93 (m, 12 AR) Weight analysis: C% H% Br / o S% Calculated 64.52 4.55 17.17 6.89 Found 64.52 4.52 17.04 6, 55

Exemple 21:Example 21:

3-(1 -(4'-Bromobiphényl-4-yl)-butyl)-4-hydroxy-2H-1 -benzopyran-2-one C25H21BrO3 PM = 449,35 OH) Br  3- (1 - (4'-Bromobiphenyl-4-yl) -butyl) -4-hydroxy-2H-1 -benzopyran-2-one C25H21BrO3 PM = 449.35 OH) Br

PFG= 161-163 CPFG = 161-163 C

IRyc=o: 1670 cm-' IRyoH: 3300 cm' 1H RMN (CDCI3) ô en ppm: 1,5 (t, CH3); 1,65 (m, CH2); 2,28 (m, CH2); 4,79 (m, CH); 6,54 (s, OH); 7,39-7,87 (m, 12 AR) Analyse pondérale: C% H% Br0/o Calculée 66,82 4,71 17,79 Trouvée 66,69 4, 79 17,64  IRyc = o: 1670 cm- 'IRyoH: 3300 cm' 1H NMR (CDCI3) ô in ppm: 1.5 (t, CH3); 1.65 (m, CH2); 2.28 (m, CH2); 4.79 (m, CH); 6.54 (s, OH); 7.39-7.87 (m, 12 AR) Weight analysis: C% H% Br0 / o Calculated 66.82 4.71 17.79 Found 66.69 4, 79 17.64

Claims (4)

REVENDICATIONS 1) 4-Hydroxy-2H-1 -(thio)pyran-2-ones de formule I:  1) 4-Hydroxy-2H-1 - (thio) pyran-2-ones of formula I: OH ROH R R3R dans laquelle: X représente O ou S, R1 représente l'hydrogène, un halogène, un radical alkoxy en C1-C6, un radical alkyle en C1-C7, un radical trifluorométhyle, un radical cyano, R2 représente l'hydrogène, un radical alkyle en C1-C7, un radical aralkyle, un radical (hétéro)aryle, un radical cyclohexyle, R3 et R4 représentent l'hydrogène, un radical alkyle en C1-C7, ou peuvent former  R3R in which: X represents O or S, R1 represents hydrogen, a halogen, a C1-C6 alkoxy radical, a C1-C7 alkyl radical, a trifluoromethyl radical, a cyano radical, R2 represents hydrogen, a C1-C7 alkyl radical, an aralkyl radical, a (hetero) aryl radical, a cyclohexyl radical, R3 and R4 represent hydrogen, a C1-C7 alkyl radical, or can form ensemble un cycle benzénique, un hétérocycle ou un groupe -(CH2)n- avec n = 3-5.  together a benzene ring, a heterocycle or a group - (CH2) n- with n = 3-5. 2) Composés selon la revendication 1 caractérisés en ce que X est un oxygène.  2) Compounds according to claim 1 characterized in that X is oxygen. 3) Composés selon la revendication 1 caractérisés en ce que X est un soufre.  3) Compounds according to claim 1 characterized in that X is a sulfur. Is 4) Composés selon la revendication 1, choisis parmi les composés suivants: 3-(4-(4-bromophényl)-benzyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1-(4'bromobiphényl-4-yl)-ethyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1(4'-bromobiphényl-4-yl)-pentyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1 (4-bromobiphényl-4-yl)-I -cyclohexyl-méthyl)-4-hydroxy-2H-1 -benzopyran2-one 3-(1-(4'-bromobiphényl-4-yl)-2-méthyl-propyl)-4-hydroxy-2H-1 benzopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 benzothiopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-2-phényl-éthyl)-4hydroxy-2H-1 -benzopyran-2-one 3-((1 -(4'-bromobiphényl-4-yl)-3-méthyl)butyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-33-diméthyl-butyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1-(4'fluorobiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 -benzopyran-2-one 3-(1 -(4'trifluorométhylbiphényl-4-yl)-éthyl)-4-hydroxy-2H-1 -benzopyran-2-one 3(1 -(4'-bromobiphényl-4-yl)-pentyl)-4-hydroxy-2H-1 -benzothiopyran-2-one 3-(1-(4'-méthylbiphényl-4-yl)-éthyl)-4-hydroxy-1 -benzopyran-2-one 3-(1 (4'-isopropylbiphényl-4-yl)-éthyl)-4-hydroxy-1 -benzopyran-2-one 3-( 1 (4'cyanobiphényl-4-yl)-éthyl)-4-hydroxy- 1 -benzopyran-2-one 3-(-1 -(4'bromobiphényl-4-yi)-3-méthyl-butyl)-4-hydroxy-2H- 1 -benzothiopyran-2- one 3-(-1 -(4'-bromobiphényl-4-yl)-propyl)-4-hydroxy-2H- 1 -benzopyran-2- one 3-(-1 -(4'-bromobiphényl-4-yl)-mréthyl)-pentyl)-4-hydroxy-2H- 1 benzopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-propyl)-4-hydroxy-2H- 1 -benzothiopyran-2-one 3-(1 -(4'-bromobiphényl-4-yl)-butyl)-4-hydroxy- 2H-1 -benzoth iopyran-2-one 3-( 1 -(4'-bromobiphényl-4-yl)-butyl)-4hydroxy-2H- 1 -benzopyra n-2-one ) Procédé de préparation des composés de formule I selon la revendication 1, qui consiste: - a faire réagir un dérivé biphénylique de formule Il Ri dans laquelle R1 a la signification donnée à la revendication 1, avec un chlorure d'acide de formule III: ci R2 III dans laquelle R2 a la signification donnée à la revendication 1, pour obtenir un composé de formule IV:  Is 4) Compounds according to claim 1, chosen from the following compounds: 3- (4- (4-bromophenyl) -benzyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1- (4 ' bromobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 (4'-bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzopyran -2-one 3- (1 (4-bromobiphenyl-4-yl) -I -cyclohexyl-methyl) -4-hydroxy-2H-1 -benzopyran2-one 3- (1- (4'-bromobiphenyl-4-yl ) -2-methyl-propyl) -4-hydroxy-2H-1 benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 benzothiopyran-2 -one 3- (1 - (4'-bromobiphenyl-4-yl) -2-phenyl-ethyl) -4hydroxy-2H-1 -benzopyran-2-one 3 - ((1 - (4'-bromobiphenyl-4- yl) -3-methyl) butyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -33-dimethyl-butyl) -4-hydroxy- 2H-1 -benzopyran-2-one 3- (1- (4'fluorobiphenyl-4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3- (1 - (4'trifluoromethylbiphenyl- 4-yl) -ethyl) -4-hydroxy-2H-1 -benzopyran-2-one 3 (1 - (4'-bromobiphenyl-4-yl) -pentyl) -4-hydroxy-2H-1 -benzothiopyran-2 -one 3- (1 - (4'-methylbiphenyl-4-yl) -ethyl) -4-hydroxy-1 -benzopyran-2-one 3- (1 (4'-isopropylbiphenyl-4-yl) -ethyl) -4-hydroxy-1 - benzopyran-2-one 3- (1 (4'cyanobiphenyl-4-yl) -ethyl) -4-hydroxy- 1 -benzopyran-2-one 3 - (- 1 - (4'bromobiphenyl-4-yi) -3 -methyl-butyl) -4-hydroxy-2H- 1 -benzothiopyran-2- one 3 - (- 1 - (4'-bromobiphenyl-4-yl) -propyl) -4-hydroxy-2H- 1 -benzopyran-2 - one 3 - (- 1 - (4'-bromobiphenyl-4-yl) -methyl) -pentyl) -4-hydroxy-2H- 1 benzopyran-2-one 3- (1 - (4'-bromobiphenyl-4- yl) -propyl) -4-hydroxy-2H- 1 -benzothiopyran-2-one 3- (1 - (4'-bromobiphenyl-4-yl) -butyl) -4-hydroxy- 2H-1 -benzoth iopyran-2 -one 3- (1 - (4'-bromobiphenyl-4-yl) -butyl) -4hydroxy-2H- 1 -benzopyra n-2-one) Process for the preparation of the compounds of formula I according to claim 1, which consists: - reacting a biphenyl derivative of formula II Ri in which R1 has the meaning given to claim 1, with an acid chloride of formula III: ci R2 III in which R2 has the meaning given to claim 1, to obtain a compound of formula IV: R1 R2R1 R2 - à réduire le composé cétonique de formule IV en alcool de formule V: OH - à condenser le composé de formule V avec une 4-hydroxy-2H-2(thio)pyran-2-one de formule VI: OH Vt R:I R4 o dans laquelle R3 et R4 ont la signification donnée à la revendication 1, pour obtenir un composé de formule I. 6) Composition rodonticide caractérisée en ce qu'elle contient comme substance active un composé suivant la revendication 1 en association avec un support consommable  - to reduce the ketone compound of formula IV to alcohol of formula V: OH - to condense the compound of formula V with a 4-hydroxy-2H-2 (thio) pyran-2-one of formula VI: OH Vt R: I R4 o in which R3 and R4 have the meaning given to claim 1, to obtain a compound of formula I. 6) Rodonticidal composition characterized in that it contains as active substance a compound according to claim 1 in association with a consumable carrier par les rongeurs.by rodents. 7) Composition rodonticide selon la revendication 6, caractérisée en ce qu'elle contient  7) Rodonticidal composition according to claim 6, characterized in that it contains comme substance active la 3-((-1-(4'-bromobiphényl-4-yl)-3-méthyl)butyl)-4-hydroxy-  as active substance 3 - ((- 1- (4'-bromobiphenyl-4-yl) -3-methyl) butyl) -4-hydroxy- 2H-1 -benzopyran-2-one.2H-1 -benzopyran-2-one.
FR9708286A 1997-07-01 1997-07-01 NOVEL 4-HYDROXY-2H-1- (THIO) PYRAN-2-ONES DERIVATIVES, THEIR PREPARATIONS AND THEIR USES AS RODONTICIDES Pending FR2765579A1 (en)

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FR9708286A FR2765579A1 (en) 1997-07-01 1997-07-01 NOVEL 4-HYDROXY-2H-1- (THIO) PYRAN-2-ONES DERIVATIVES, THEIR PREPARATIONS AND THEIR USES AS RODONTICIDES
MA25140A MA24582A1 (en) 1997-07-01 1998-06-24 NOVEL 4-HYDROXY-2H-1- (THIO) PYRAN-2-ONES DERIVATIVES, THEIR PREPARATIONS AND THEIR USES AS RODONTICIDES.
TNTNSN98119A TNSN98119A1 (en) 1997-07-01 1998-06-30 NOVEL 4-HYDROXY-2H-1- (THIO) PYRAN-2-ONES DERIVATIVES, THEIR PREPARATIONS AND THEIR USES AS RODONTICIDES.
PCT/FR1998/001412 WO1999001446A1 (en) 1997-07-01 1998-07-01 Novel 4-hydroxy-2h-1-(thio)pyran-2-ones derivatives and their use as rat poison
AU84455/98A AU8445598A (en) 1997-07-01 1998-07-01 Novel 4-hydroxy-2h-1-(thio)pyran-2-ones derivatives and their use as rat poison

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WO2002085882A1 (en) * 2001-04-24 2002-10-31 Arxy Therapeutics Coumarin derivatives to be used as anticoagulants
US7145020B2 (en) 2001-04-24 2006-12-05 Aryx Therapeutics Materials and methods for treating coagulation disorders

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AU2003209990B8 (en) * 2002-02-25 2008-10-30 Kudos Pharmaceuticals Ltd Pyranones useful as ATM inhibitors
GB0211018D0 (en) * 2002-05-14 2002-06-26 Syngenta Ltd Novel compounds
GB0211019D0 (en) * 2002-05-14 2002-06-26 Syngenta Ltd Novel compounds
FR2956402B1 (en) * 2010-02-18 2012-03-09 Liphatech Inc RODENTICIDE COMPOUND, COMPOSITION INCLUDING THE SAME AND USE FOR CONTROLLING HARMFUL RODENTS

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002085882A1 (en) * 2001-04-24 2002-10-31 Arxy Therapeutics Coumarin derivatives to be used as anticoagulants
US6864279B2 (en) 2001-04-24 2005-03-08 Aryx Therapeutics Materials and methods for treating coagulation disorders
US7145020B2 (en) 2001-04-24 2006-12-05 Aryx Therapeutics Materials and methods for treating coagulation disorders

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